EP0908468B1 - Verfahren zur (Co)Polymerisation von Olefinen - Google Patents

Verfahren zur (Co)Polymerisation von Olefinen Download PDF

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Publication number
EP0908468B1
EP0908468B1 EP98124378A EP98124378A EP0908468B1 EP 0908468 B1 EP0908468 B1 EP 0908468B1 EP 98124378 A EP98124378 A EP 98124378A EP 98124378 A EP98124378 A EP 98124378A EP 0908468 B1 EP0908468 B1 EP 0908468B1
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Prior art keywords
process according
neutral metallocene
catalytic
metallocene
catalytic solid
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French (fr)
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EP0908468A3 (de
EP0908468A2 (de
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Nicola Zandona
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Ineos Manufacturing Belgium NV
Solvay SA
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Solvay Polyolefins Europe Belgium SA
Solvay SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61904—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with another component of C08F4/60
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the present invention relates to a (co) polymerization process olefins, using a catalytic system based on an ionic metallocene derived from a transition metal and an aluminum derivative.
  • Patent application EP-500944 discloses a process for the polymerization of alpha-olefins in which operates a catalytic system obtained by reacting a compound organoaluminum with a neutral halogenated metallocene derived from a metal of transition and the product thus obtained is mixed with an ionizing agent such as tetrakis (pentafluorophenyl) triphenylcarbenium borate.
  • This known method has the drawback, when ethylene is polymerized, to cause crusting in the polymerization installations. Furthermore, it does not make it possible to obtain polymers having a broad, distribution of molecular weights and high apparent specific gravity.
  • the invention overcomes the aforementioned drawbacks by providing a method for the polymerization of olefins using a catalytic system of constitution new which reduces the risk of crusting during its use and which allows moreover to obtain polymers characterized by an apparent specific weight higher and fine tune the weight distribution of the (co) polymers obtained.
  • the invention relates to a process for (co) polymerization of at least one olefin in the presence of a catalytic system comprising at least one aluminum derivative of general formula AlX n T 3-n , in which X denotes a halogen, T denotes a hydrocarbon radical which can optionally include oxygen and n is a number from 0 to 3, at least one ionizing agent and at least one neutral metallocene derived from a transition metal, according to which a mixture is prepared neutral metallocene with a catalytic solid containing at least one element from group IVB of the periodic table, magnesium and a halogen, the mixture thus obtained is brought into contact with at least one hydrocarbon diluent, the aluminum derivative and the olefin, and the ionizing agent is added thereto.
  • a catalytic system comprising at least one aluminum derivative of general formula AlX n T 3-n , in which X denotes a halogen, T denotes a hydrocarbon radical which
  • the aluminum derivative of general formula AlX n T 3-n can for example be chosen from trialkylaluminum and haloalkylaluminum compounds.
  • Preferred aluminum derivatives are those in which the group T is a hydrocarbon radical chosen from optionally substituted alkyl, alkenyl, aryl and alkoxy groups containing up to 20 carbon atoms, such as tributyl-, trimethyl-, triethyl-, tripropyl-, triisopropyl-, triisobutyl-, trihexyl-, trioctyl- and tridodecylaluminium and diethylaluminum chloride.
  • the most advantageous aluminum derivatives are triethylaluminum and triisobutylaluminum.
  • the transition metal of the metallocene can advantageously be a element selected from scandium, titanium, zirconium, hafnium and vanadium. Zirconium is preferred.
  • the groups Cp and Cp 'each advantageously represent a group mono- or polycyclic comprising from 5 to 50 carbon atoms linked by double conjugate bonds.
  • non-halogenated, mono- and dihalogenated scandium metallocenes such as methyldi (cyclopentadienyl) scandium, chloro (cyclopentadienyl) ) ethylscandium, chlorodi (cyclopentadienyl) scandium and dichloro (indenyl) scandium, non-halogenated, mono-, di- and trihalogenated titanium metallocenes such as diethyldi (fluorenyl) titanium, dibromo (methylcyclopentadienyl) butyltitane, chloro ( indenyl) diisopropyltitanium, chloromethyldi (pentamethylcyclopentadienyl) titanium, dibromodi (methylcyclopentadienyl) titanium and trichloro (cyclopen
  • the neutral metallocenes of formula (C p ) a (C p ') b MX x Z z can for example be chosen from those comprising as silyl radical, allyldimethylchlorosilyl, allylmethyldiethoxysilyl, 5- (dicycloheptenyl) trichlorosilyl, 2-bromo-3-trimethylsilyl-1-propenyl, 3-chloropropyldimethylvinylsilyl, 2- (3 -cyclohexenyl) ethyltrimethoxysilyl and diphenylvinylchlorosilyl.
  • the metallocenes having a covalent bridge connecting the two groups C p and C p ' can be chosen from those of general formula: wherein A represents an alkylene group which may optionally include oxygen, alkenylene, arylalkylene, alkylarylene, arylalkenylene, optionally halogenated or a radical derived from an element chosen from groups IIIA, IVA, VA and VIA of the periodic table, such as boron, aluminum, silicon, germanium, tin, nitrogen, phosphorus or sulfur.
  • bridged metallocenes we can cite those corresponding to the formulas: in which Ind represents the indenyl radical, Cyc represents the cyclopentadienyl radical and Cyc * represents the pentamethylcyclopentadienyl radical.
  • the preferred metallocenes of formula (C p ) a (C p ') b MX x Z z are those in which the groups C p and C p ' are chosen from cyclopentadienyl, indenyl and fluorenyl radicals. Good results are obtained with those in which the groups Cp and Cp 'are linked by a covalent bridge of the alkyl type.
  • Metallocenes whose transition metal is chosen from titanium, zirconium and hafnium are very suitable. Particularly satisfactory results are obtained with metallocenes derived from zirconium.
  • the catalytic solid is a catalyst for the polymerization of olefins, obtained by mixing a magnesium compound with a compound of an element from group IVB of the periodic table and a halogenated compound.
  • the compound halogenated may optionally be an integral part of the magnesium compound or the compound of the group IVB element.
  • magnesium compounds usable for the preparation of the solid catalytic there may be mentioned, by way of nonlimiting examples, the halides, hydroxide, oxide, hydroxyhalides, alcoholates, haloalcoholates, aryl alcoholates, haloaryl alcoholates, magnesium alkyl halides and their mixtures.
  • Compounds of element of group IVB of the periodic table which can be used for the synthesis of the catalytic solid are tetrahalides, alcoholates, halogenated alcoholates, trihalides obtained by reduction of tetrahalides by means of an organoaluminum compound, or mixtures thereof.
  • Examples include TiCl 4 , Zr (OC 2 H 5 ) Cl 3 , Hf (OC 4 H 9 ) 2 Cl 2 and Ti (OC 2 H 5 ) 3 Br.
  • the halogenated compound in the case where the halogenated compound is not an integral part of the magnesium compound or of the compound of the element of group IVB, it can for example be chosen from halogenated aluminum derivatives of formula AlT y X 3-y in which T represents a hydrocarbon radical which may optionally include oxygen, y denotes an integer from 0 to 2 and X represents a halogen.
  • T represents a hydrocarbon radical which may optionally include oxygen
  • y denotes an integer from 0 to 2
  • X represents a halogen.
  • the halogenated compound can also be selected from halogenated silicon derivatives such as for example SiCl 4 , (C 2 H 5 O) 2 SiCl 2 or (CH 3 ) 3 SiCl.
  • the manufacture of the catalytic solid can also involve the employment of an electron donor such as carboxylic acids, esters, ethers and alcohols.
  • This electron donor is generally chosen from those containing up to 12 carbon atoms. It is advantageously used for pretreat the magnesium compound.
  • a typical example of synthesis of the catalytic solid consists in mix a halide from element of group IVB of the periodic table with an oxygenated magnesium compound as described in patents BE-705220 (SOLVAY & CIE) and BE-730068 (SOLVAY & CIE).
  • a mixture of an oxygenated compound of the group IVB element is precipitated and of an oxygenated magnesium compound by means of a halogenated compound, such as described in patent BE-791676 (SOLVAY).
  • Preferred catalytic solids are those with the group IVB element is titanium and whose halogen is chlorine.
  • the best results are obtained with the catalytic solids having an element content of group IVB of 10 to 30% by weight, preferably 15 to 20%, typically around 17%, a halogen content of 20 to 50% by weight, the values of 30 to 40% (in about 36%) being preferred and a magnesium content of 0.5 to 20% by weight, usually from 1 to 10%, for example about 5%.
  • Catalytic systems which can be used according to the invention having led to good results are those with a transition metal weight ratio to the element of group IVB of the catalytic solid at least equal to 0.05, of preferably 0.1, for example 0.5; it is usually at most equal to 10, in particular to 5, for example to 2.
  • the catalytic system comprises a mineral support.
  • the mineral support can be selected from oxides minerals such as oxides of silicon, aluminum, titanium, zirconium, of thorium, their mixtures and the mixed oxides of these metals such as silicate aluminum and aluminum phosphate, and among the mineral halides such than magnesium chloride. Silica, alumina, magnesium chloride and mixtures of silica and magnesium chloride are preferred.
  • the term “ionizing agent” is intended to denote a compound comprising a first part which has the properties of a Lewis acid and which is capable of ionizing the neutral metallocene and a second part which is inert towards the ionized metallocene and which is capable of stabilize the ionized metallocene.
  • the ionizing agent can be an ionic compound comprising a cation having the properties of a Lewis acid and an anion constituting the aforementioned second part of the ionizing agent.
  • the anions having leads to very good results are organoborates. We mean by organoborate a boron derivative in which the boron atom is linked to 4 organic substituents.
  • ionizing agents examples include ionic triphenylcarbenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate of N, N-dimethylanilinium and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate.
  • the acids of Lewis cationic preferred are carbenium, sulfonium and oxonium.
  • the ionizing agent can also be a nonionic compound exhibiting the properties of a Lewis acid which is capable of transforming the neutral metallocene in cationic metallocene.
  • the ionizing agent is itself transformed into an anion inert towards the cationic metallocene which is able to stabilize it.
  • ionizing agent nonionic tri (pentafluorophenyl) boron, triphenylboron, trimethylboron, tri (trimethylsilyl) borate and organoboroxins. Ionizing agents nonionics are used in the absence of a Brönsted acid.
  • the ionizing agent is preferably selected from tetrakis (pentafluorophenyl) borate of triphenylcarbenium and the tri (pentafluorophenyl) boron.
  • the first step in the process of preparing the catalytic system consists in mixing the neutral metallocene with the catalytic solid.
  • This mixture can be carried out dry by mixing the constituents in the solid state. he can also be produced by impregnating the catalytic solid with a solution of the neutral metallocene in a hydrocarbon diluent. Suspension thus obtained can be used as is in the next step. Alternatively, the catalytic solid impregnated with neutral metallocene can be collected from the suspension and used in the next step in the solid state.
  • This first step can be carried out at any temperature below the decomposition temperature of the neutral metallocene and of the catalytic solid.
  • the temperature is usually between room temperature and 100 ° C, preferably 50 to 85 ° C.
  • the neutral metallocene and the catalytic solid are advantageously used in quantities such as the ratio by weight of the neutral metallocene to the catalytic solid is generally at least equal to 0.01, in particular to 0.1; it is usually at most 20, preferably 10, values from 0.3 to 5, typically about 2, being the most advantageous.
  • the mixture prepared during the first stage of the preparation of a catalytic system according to the invention may comprise more than one neutral metallocene and more than one catalytic solid.
  • the second step in the process of preparing the catalytic system consists in bringing the mixture obtained in the first step into contact with the derivative aluminum in at least one hydrocarbon diluent and with the ionizing agent.
  • the aluminum derivative has the function of serving as a co-catalyst of the system catalytic during its use for the polymerization of olefins.
  • the neutral metallocene used in the first stage is halogenated
  • the aluminum derivative comprises at least one hydrocarbon radical.
  • the aluminum derivative also has the function of substituting, in the second stage of the process according to the invention, at least one of the halogens of the neutral metallocene by a hydrocarbon radical.
  • the aluminum derivative is added first to the mixture derived from the first step, then the ionizing agent.
  • the aluminum derivative is advantageously added when using the catalytic system in the process for the polymerization of olefins.
  • the hydrocarbon diluent that can be used in this second step can be chosen from aliphatic hydrocarbons such as linear alkanes (by example n-butane, n-hexane and n-heptane), branched alkanes (for example isobutane, isopentane, isooctane and 2,2-dimethylpropane), cycloalkanes (e.g. cyclopentane and cyclohexane), among the monocyclic aromatic hydrocarbons such as benzene and its derivatives, for example example toluene, and among polycyclic aromatic hydrocarbons, each cycle can be substituted.
  • aliphatic hydrocarbons such as linear alkanes (by example n-butane, n-hexane and n-heptane), branched alkanes (for example isobutane, isopentane, isooctane and 2,2-dimethylpropane),
  • the amount of the aluminum derivative used in the second step depends on the choice of these compounds. In practical, in the case where the neutral metallocene is halogenated, it is advantageous to use the aluminum derivative in an amount sufficient to replace all of the neutral metallocene halogen atoms. D may be advantageous to use higher amounts of the aluminum derivative to benefit from its properties of impurity sensor during the production of the catalytic system. In this effect, it is recommended for example that the molar ratio of the aluminum derivative neutral metallocene is at least equal to 10.
  • the molar ratio of the aluminum derivative to neutral metallocene is at least 100. In principle, there is no limit greater than the aforementioned molar ratio. In practice, however, there is no point in what this ratio exceeds 5000 for economic reasons the values less than 2000 being recommended. Values close to 500 to 1000 generally work well.
  • the ionizing agent is preferably used in an amount sufficient to ionize the entire metallocene.
  • the amount of ionizing agent to to implement will therefore depend on the neutral metallocene and the agent ionizing agents selected.
  • an amount of ionizing agent can be used such as the molar ratio of the ionizing agent to the neutral metallocene set work in the first step mentioned above is at least equal to 0.1, in particular at less than 0.5, values not exceeding 10 being preferred, those not not exceeding 2 being recommended.
  • This second stage of the process for preparing the catalytic system can be performed at any temperature that is both lower than the temperature of boiling of the most volatile compound of the medium obtained at working pressure and lower than the thermal decomposition temperature of the components of the middle.
  • medium is meant to designate all of the components used in the second stage (neutral metallocene, catalytic solid, aluminum derivative, hydrocarbon diluent and ionizing agent) and collected at the end thereof.
  • the temperature therefore depends on the nature of the components of the medium and is generally greater than -50 ° C, preferably at least equal to 0 ° C. She is usually at most equal to 100 ° C, preferably less than 80 ° C.
  • the ambient temperature is particularly suitable.
  • the duration of this second stage must be sufficient to obtain a complete ionization of the metallocene or of the product of its reaction with the derivative aluminum. It can vary from a few seconds to several hours.
  • the reactions to the second stage are generally almost instantaneous, the durations of 0.5 to 30 minutes are the most common.
  • the medium can be agitated throughout the duration of the second stage or during part of it.
  • the first step is carried out by dry process by mixing the catalytic solid and neutral metallocene in the solid state and the mixture is put solid thus obtained in use in the second step.
  • the metallocene neutral and the catalytic solid are ground together in the solid state while mix them.
  • the catalytic solid is impregnated with a solution of neutral metallocene.
  • a solution of neutral metallocene for this purpose, it is dissolved beforehand in a hydrocarbon aromatic, preferably toluene.
  • the solid impregnated catalyst is collected from the suspension and used in the solid state in the next step.
  • a solid is collected resulting from the contacting of the aluminum derivative with the mixture from the first step and add then the ionizing agent to this solid.
  • the ionizing agent in the solid state or in the liquid state, for example in the state of a solution.
  • the second step of the process is preceded by a dissolution of the agent ionizing in a hydrocarbon diluent.
  • the hydrocarbon diluent can be selected from aromatic hydrocarbons such as toluene and halogenated aliphatic hydrocarbons such as methylene chloride and chloroform. Toluene works well.
  • the quantity of the hydrocarbon diluent used must be sufficient to allow complete dissolution of the ionizing agent. The amount of the diluent hydrocarbon therefore depends on its nature, the nature of the ionizing agent and the temperature at which the second step of the process is carried out.
  • the neutral metallocene is deposited on a mineral support.
  • the mineral support can be selected from mineral oxides such as oxides of silicon, aluminum, titanium, zirconium, thorium, their mixtures and mixed oxides of these metals such as aluminum silicate and aluminum phosphate, and among metal halides such as magnesium chloride. Silica, alumina, magnesium chloride and mixtures of silica and magnesium chloride are preferred.
  • this fifth embodiment we permeates the mineral support, possibly activated beforehand by any means known, with a solution of neutral metallocene.
  • the solution can be prepared as in the second embodiment of the method, explained above.
  • the operating temperature of the impregnation may vary from ambient temperature at the boiling temperature of the neutral metallocene solution and the duration of the impregnation can vary from a few minutes to several hours.
  • the mineral support impregnated with neutral metallocene is collected from the suspension and then mixed with the catalytic solid during the first step explained above.
  • the mineral support and neutral metallocene are mixed in the solid state (possibly by co-grinding them).
  • the solid mixture thus obtained is then implemented in the first step explained above.
  • the ionizing agent is deposited on a mineral support.
  • the mineral support is impregnated, possibly activated beforehand by any known means, with a solution of the ionizing agent.
  • the solution may be prepared as in the fourth embodiment of the method according to the invention explained above.
  • the mineral support and the operating conditions of the impregnation are in accordance with what has been described above in the fifth embodiment of the method according to the invention.
  • a seventh embodiment of the process for preparing the particularly efficient catalytic system mixed in the dry state the catalytic solid with an inorganic support and the mixture thus obtained is put implemented in the first step of the method according to the invention.
  • the mineral support conforms to that used in the fifth embodiment of the process explained above.
  • a neutral metallocene of formula (C p ) a (C p ') b MX x (-R t- Si-R'R''R '') z which was prepared by reacting with a silane a compound of formula (C p ) a (C p ') b MX x H z where the symbols Cp, Cp ', M, X, H , a, b, x and z have the same meaning as that given above, except for z which is greater than zero.
  • the reaction is preferably carried out in a suitable solvent.
  • silanes which can be used in this embodiment include allyldimethylchlorosilane, allylmethyldiethoxysilane, 5- (dicycloheptenyl) trichlorosilane, 2-bromo-3-trimethylsilyl-1-propene, 3-chloropropyldimethylvinylsilane, 2- (3-cyclohexenyl) ethyltrimethoxysilane, diphenylvinylchlorosilane, vinyltriphenoxysilane, vinyltrichlorosilane, 2- (trimethylsilylmethyl) -1,3-butadiene and 3- (trimethylsilyl) cyclopentene.
  • the preferred silanes are the non-chlorinated alkenylsilanes such as allyltriethoxysilane, allyltrimethylsilane, 5- (bicycloheptenyl) triethoxysilane, vinyl (trimethoxy) silane and 2- (3-cyclohexenyl) ethyltrimethoxysilane. Vinyl (trimethoxy) silane is particularly suitable.
  • the solvent for the reaction between the silane and the compound of formula (C p ) a (C p ') b MX x H z is advantageously an aromatic hydrocarbon, preferably toluene.
  • the temperature at which this reaction is carried out can vary from room temperature to the boiling point of the solvent used, for example from 20 to 100 ° C. The preferred temperature is room temperature.
  • a neutral metallocene of formula (C p ) a (C p ') b MX x Z z is used , where the symbols Cp, Cp', M, X, Z, a, b, x and z have the same meaning as that given above, in which z is different from 0 and Z is a hydrocarbon radical which has been prepared by reacting a compound of formula (C p ) a (C p ') b MX x H z with an olefin. This reaction preferably takes place in a suitable solvent.
  • the compounds of formula (C p ) a (C p ') b MX x H z conform to those defined above in the eighth embodiment.
  • the olefins which can be used in this embodiment advantageously contain up to 20 carbon atoms, preferably up to 12 carbon atoms, and can be chosen from mono-olefins such as ethylene and 3-ethyl-1 -butene, unconjugated diolefins such as 1,5-hexadiene, conjugated diolefins such as 1,3-pentadiene and alicyclic diolefins such as dicyclopentadienyl.
  • the preferred olefin is ethylene.
  • the solvent for the reaction between the olefin and the compound of formula (C p ) a (C p ') b MX x H z is advantageously an aromatic hydrocarbon, preferably toluene.
  • the temperature at which this reaction is carried out can vary from room temperature to the boiling point of the solvent used, for example from 20 to 100 ° C. The preferred temperature is room temperature.
  • the process of preparing the catalytic system makes it possible to obtain mixed catalytic systems based on an ionic metallocene and a solid catalytic containing at least one element of group IVB of the periodic table, magnesium and halogen.
  • the catalytic system can be used in the process according to the invention, for homopolymerization and copolymerization of olefins containing up to 20 carbon atoms per molecule.
  • the olefins advantageously contain 2 with 12 carbon atoms per molecule and are for example chosen from ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3- and 4-methyl-1-pentenes, 1-octene, 3-ethyl-1-butene, 1-heptene, 3,4-dimethyl-1-hexene, 4-butyl-1-octene, 5-ethyl-1-decene and 3,3-dimethyl-1-butene, and vinyl monomers such as styrene.
  • the catalytic systems find particular use in production homopolymers of ethylene and propylene, or copolymers of ethylene and propylene with one or more olefinically unsaturated comonomers.
  • the comonomers can be of various materials. They can be mono-olefins up to 8 carbon atoms, for example the 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3- and 4-methyl-1-pentenes and 1-octene.
  • One or more diolefins comprising of 4 to 18 carbon atoms can also be copolymerized with ethylene and propylene.
  • the diolefins are chosen from diolefins non-conjugated aliphatics such as 4-vinylcyclohexene and 1,5-hexadiene, alicyclic diolefins having an endocyclic bridge such as dicyclopentadiene, methylene- and ethylidene-norbornene, and diolefins aliphatic conjugates such as 1,3-butadiene, isoprene and 1,3-pentadiene.
  • diolefins non-conjugated aliphatics such as 4-vinylcyclohexene and 1,5-hexadiene
  • alicyclic diolefins having an endocyclic bridge such as dicyclopentadiene, methylene- and ethylidene-norbornene
  • diolefins aliphatic conjugates such as 1,3-butadiene, isoprene and 1,3-pentadiene
  • the catalytic system appears to be particularly efficient for manufacture of ethylene or propylene homopolymers, and copolymers ethylene or propylene containing at least 90%, preferably at least 95%, by weight of ethylene or propylene.
  • the favorite comonomers of ethylene are propylene, 1-butene, 1-hexene, 1-octene and 1,5-hexadiene, and those of propylene are ethylene, 1,3-butadiene, 1,5-hexadiene.
  • the derivative aluminum, neutral metallocene, ionizing agent, catalytic solid and hydrocarbon diluent conform to those used in the process preparation of the catalytic system explained above.
  • isobutane or hexane as a hydrocarbon diluent. Isobutane is suitable particularly well.
  • the olefin is conforms to the definition provided above of polymerizable olefins in presence of catalytic systems.
  • the preparation of the mixture of the neutral metallocene and the catalytic solid, and the addition of the agent ionizing are carried out respectively as in the first and second step in the process for preparing the catalytic system described above, preferably in the polymerization reactor.
  • chains polymers are formed in the presence of the catalytic solid, activated by the derivative of aluminum playing the role of cocatalyst. This chain formation polymeric continues until the exhaustion of the activity of the catalytic solid and / or the olefin feed. Furthermore, as soon as the ionizing agent is added in the polymerization reactor, another type of polymer chain is formed catalyzed by the ionic metallocene (activated by the aluminum derivative and by the ionizing agent).
  • the final polymer product consists of at least two types of polymer chains in proportions that can be made vary according to the quantities of the catalytic solid, the neutral metallocene and the ionizing agent used and according to the moment of introduction of the agent ionizing.
  • the mixture of the neutral metallocene and the solid is first put catalytic in contact with the aluminum derivative in the reactor polymerization and then the olefin is introduced.
  • putting in contact with the organoaluminum compound can be performed as in the second step in the process for preparing the catalytic system described above.
  • the derivative of aluminum and the olefin are brought into contact with the mixture of the metallocene neutral and catalytic solid simultaneously by introducing them at the same time in the polymerization reactor, and then the ionizing agent is added to it.
  • the ionizing agent is introduced in the polymerization reactor after the activity of the catalytic solid is reduced by at least 50%, preferably by at least 75% of its initial value.
  • activity of the catalytic solid is intended to denote the amount of polymer obtained, expressed in grams, in the presence of the catalytic solid per hour and by gram of catalytic solid.
  • the neutral metallocene is used and the catalytic solid in amounts such as the weight ratio of metallocene neutral to the catalytic solid, ie from 1 to 20.
  • This variant of the invention is particularly advantageous when it is desired to limit the crusting phenomena in the polymerization reactor and favor the formation of (co) polymers of high apparent specific gravity. Indeed, because of the small quantity of catalytic solid relative to that of the metallocene, this variant allows, after the introduction of the olefin and before adding the ionizing agent, to coat the catalytic sites of the metallocene, which does not will be activated only when the ionizing agent is added, thus leading to advantages mentioned above.
  • the neutral metallocene is used and the catalytic solid in amounts such as the molar ratio of the metallocene neutral to the solid catalyst is from 0.01 to 1. This embodiment appears particularly effective when it is desired to obtain (co) polymers having a wide molecular weight distribution while limiting their content oligomers.
  • the neutral metallocene or the ionizing agent is deposited on a mineral support.
  • the mineral support conforms to that used in the fifth embodiment of the system preparation process Catalytic.
  • the mineral support is impregnated with a solution of neutral metallocene (respectively of the ionizing agent) as described in the second (respectively the fourth) embodiment of the process for preparing the catalytic system.
  • the mineral support and the neutral metallocene are mixed (possibly by co-grinding them) in the solid state.
  • the solid catalytic is mixed with an inorganic support before putting this mixture into contact with neutral metallocene.
  • the mineral support conforms to that used as a support for the neutral metallocene described above.
  • the polymerization can be carried out either in solution, in suspension or in the gas phase and can be carried out continuously or discontinuously, for example by carrying out the polymerization in one or more reactors.
  • Another way to do it consists of working in several reactors arranged in series, the solid catalytic being activated in the first reactor and the metallocene in a next reactor.
  • the process thus carried out proves to be particularly efficient for the manufacture of (co) polymers having a molecular weight distribution multimodal, in particular bimodal.
  • a molecular weight regulator such as hydrogen.
  • a variant of the (co) polymerization process according to the invention includes a prepolymerization in suspension in a first reactor followed of a gas phase polymerization in a second reactor.
  • a (co) polymerization in suspension this is carried out in a hydrocarbon diluent such as those which can be used in the preparation of mixture of neutral metallocene and aluminum derivative, and at a temperature such that at least 50% (preferably at least 70%) of the (co) polymer formed y is insoluble.
  • the temperature is generally at least 20 ° C, from preferably at least 50 ° C; it is usually at most equal to 200 ° C., preferably at most 100 ° C.
  • the partial pressure of olefin is the most often at least equal to atmospheric pressure, preferably ⁇ 0.4 MPa, for example ⁇ 0.6 MPa; this pressure is generally at most equal to 5 MPa, preferably ⁇ 2 MPa, for example ⁇ 1.5 MPa.
  • a (co) polymerization in solution this can be carried out in a hydrocarbon diluent such as those mentioned above.
  • the operating temperature depends on the hydrocarbon diluent used and must be higher than the dissolution temperature of the (co) polymer in it, so that at least 50% (preferably at least 70%) of the (co) polymer is dissolved therein.
  • the temperature must be low enough to prevent a thermal degradation of the (co) polymer and / or of the catalytic system. In generally, the optimum temperature is 100-200 ° C.
  • Partial pressure olefin is most often at least equal to atmospheric pressure, preferably ⁇ 0.4 MPa, for example ⁇ 0.6 MPa; this pressure is usually at maximum equal to 5 MPa, preferably ⁇ 2 MPa, for example ⁇ 1.5 MPa.
  • the (co) polymerization is carried out using the olefin itself as a hydrocarbon diluent.
  • an olefin can be used liquid under normal pressure and temperature conditions, or operate under sufficient pressure for a normally gaseous olefin to be liquefied.
  • the partial pressure of the olefin may be less than or greater than atmospheric pressure, the preferred partial pressure varying from pressure atmospheric at around 7 MPa. In general, a pressure of 0.2 to 5 MPa is fine.
  • the choice of temperature is not critical, it is in general from 30 to 200 ° C. It is optionally possible to use a dilution gas which must be inert towards the (co) polymer.
  • a particular embodiment of the (co) polymerization process according to the invention consists in copolymerizing at least two olefins introduced simultaneously or delayed in the polymerization reactor, the two olefins preferably being introduced before the addition of the ionizing agent.
  • the (co) polymerization process according to the invention is particularly efficient for the manufacture of homopolymers of ethylene or propylene and of (co) polymers of ethylene and / or propylene.
  • Examples 1 to 3 are in accordance with the invention.
  • Examples 4 and 5 are comparative examples.
  • Example 1 (according to the invention):
  • Example 3 (according to the invention):
  • Silica of the MS3040 type from the company PQ was calcined at 600 ° C. for 16 hours in dry air and then mixed with a quantity of magnesium dichloride such that the mixture comprises 9.8% by weight of magnesium. The mixing was carried out in a rotary oven for 16 hours at 400 ° C under nitrogen.
  • Silica type 948 from the company GRACE was calcined at 800 ° C. for 16 hours under nitrogen sweep.
  • Example 5 A comparison of the results of Examples 1 and 2 with those of Example 5 shows the progress made by the invention in what relates to the distribution of the molecular weights of the polymer obtained.

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Claims (24)

  1. Verfahren zur (Co)polymerisation von wenigstens einem Olefin in Gegenwart eines katalytischen Systems, umfassend wenigstens ein Aluminiumderivat der allgemeinen Formel AlXnT3-n, worin X ein Halogen bezeichnet, T einen Kohlenwasserstoffrest, der gegebenenfalls Sauerstoff umfassen kann, bezeichnet und n eine Zahl von 0 bis 3 ist, wenigstens ein Ionisierungsmittel und wenigstens ein neutrales Metallocen, das von einem Übergangsmetall abgeleitet ist, gemäß dem man ein Gemisch des neutralen Metallocens mit einem katalytischen Feststoff, der wenigstens ein Element der Gruppe IVB des Periodensystems, Magnesium und ein Halogen enthält, herstellt, man das so erhaltene Gemisch mit wenigstens einem Kohlenwasserstoffverdünnungsmittel, dem Aluminiumderivat und dem Olefin in Kontakt bringt und man dazu das Ionisierungsmittel hinzufügt.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass das Olefin Ethylen und/oder Propylen ist.
  3. Verfahren gemäß Anspruch 1 bis 2, dadurch gekennzeichnet, dass das neutrale Metallocen der Formel (Cp)a(Cp')bMXxZz entspricht, worin:
    Cp und Cp' jeweils einen ungesättigten Kohlenwasserstoffrest, der an ein Zentralatom koordiniert ist, bezeichnen, wobei die Gruppen Cp und Cp' über eine kovalente Brücke verbunden sein können,
    M das Übergangsmetall bezeichnet, das unter den Gruppen IIIB, IVB, VB und VIB des Periodensystems ausgewählt ist,
    a, b, x und z ganze Zahlen bedeuten, so dass (a + b + x + z) = m, x ≥ 0, z ≥ 0 und a und/oder b ≠ 0,
    m die Wertigkeit des Übergangsmetalls M bezeichnet,
    X ein Halogen bezeichnet,
    Z einen Kohlenwasserstoffrest, der gegebenenfalls Sauerstoff umfassen kann, oder einen Silylrest der Formel (-Rt-Si-R'R''R''') bezeichnet, worin
    R eine gegebenenfalls substituierte Alkyl-, Alkenyl-, Aryl-, Alkoxy- oder Cycloalkylgruppe mit bis zu 20 Kohlenstoffatomen bezeichnet,
    R', R" und R''' gleich oder verschieden sind und jeweils ein Halogen oder eine gegebenenfalls substituierte Alkyl-, Alkenyl-, Aryl-, Alkoxy- oder Cycloalkylgruppe mit bis zu 20 Kohlenstoffatomen bezeichnen,
    t 0 oder 1 bedeutet.
  4. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, dass das neutrale Metallocen hergestellt wird, indem man eine Verbindung der Formel (Cp)a(Cp')bMXxHz mit einem Silan umsetzt.
  5. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, dass das neutrale Metallocen hergestellt wird, indem man eine Verbindung der Formel (Cp)a(Cp')bMXxHz mit einem Olefin umsetzt.
  6. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, dass das Olefin Ethylen ist.
  7. Verfahren gemäß einem der Ansprüche 3 bis 6, dadurch gekennzeichnet, dass das Übergangsmetall Zirkonium ist.
  8. Verfahren gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass in dem katalytischen Feststoff der Gehalt an Element der Gruppe IVB 10 bis 30 Gew.-% beträgt, der Gehalt an Halogen 20 bis 50 Gew.-% beträgt und der Gehalt an Magnesium 0,5 bis 20 Gew.-% beträgt.
  9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das Ionisierungsmittel aus der Gruppe ausgewählt ist, die Triphenylcarbeniumtetrakis(pentafluorphenyl)borat, N,N-Dimethylanilinium-tetrakis(pentafluorphenyl)borat, Tri(n-butyl)ammonium-tetrakis(pentafluorphenyl)borat, Tri(pentafluorphenyl)bor, Triphenylbor, Trimethylbor, Tri(trimethylsilyl)borat und die Organoboroxine enthält.
  10. Verfahren gemäß Anspruch 9, dadurch gekennzeichnet, dass das lonisierungsmittel unter Triphenylcarbenium-tetrakis(pentafluorphenyl)borat und Tri(pentafluorphenyl)bor ausgewählt ist.
  11. Verfahren gemäß Anspruch 10, dadurch gekennzeichnet, dass das Tri(pentafluorphenyl)bor in Abwesenheit einer Brönstedsäure eingesetzt wird.
  12. Verfahren gemäß einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass das Aluminiumderivat unter denjenigen ausgewählt ist, bei denen die Gruppe T ein Kohlenwasserstoffrest ist, der ausgewählt ist unter den gegebenenfalls substituierten Alkyl-, Alkenyl-, Aryl- und Alkoxygruppen mit bis zu 20 Kohlenstoffatomen.
  13. Verfahren gemäß Anspruch 12, dadurch gekennzeichnet, dass das Aluminiumderivat unter Triethylaluminium und Triisobutylaluminium ausgewählt ist.
  14. Verfahren gemäß einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass das Kohlenwasserstoffverdünnungsmittel unter den aliphatischen Kohlenwasserstoffen ausgewählt ist.
  15. Verfahren gemäß einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass das neutrale Metallocen und der katalytische Feststoff in solchen Mengen eingesetzt werden, dass das Gewichtsverhältnis des neutralen Metallocens zu dem katalytischen Feststoff wenigstens gleich 0,01 und höchstens gleich 20 ist.
  16. Verfahren gemäß einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass das neutrale Metallocen und der katalytische Feststoff in solchen Mengen eingesetzt werden, dass das Gewichtsverhältnis des neutralen Metallocens zu dem katalytischen Feststoff 1 bis 20 beträgt.
  17. Verfahren gemäß einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass das neutrale Metallocen und der katalytische Feststoff in solchen Mengen eingesetzt werden, dass das Molverhältnis des neutralen Metallocens zu dem katalytischen Feststoff 0,01 bis 1 beträgt.
  18. Verfahren gemäß einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass das Ionisierungsmittel und das neutrale Metallocen in solchen Mengen eingesetzt werden, dass das Molverhältnis des Ionisierungsmittels zu dem neutralen Metallocen 0,1 bis 10 beträgt.
  19. Verfahren gemäß einem der Ansprüche 1 bis 18, dadurch gekennzeichnet, dass das Aluminiumderivat und das neutrale Metallocen in solchen Mengen eingesetzt werden, dass das Molverhältnis des Aluminiumderivats zu dem neutralen Metallocen wenigstens gleich 10 ist.
  20. Verfahren gemäß einem der Ansprüche 1 bis 19, dadurch gekennzeichnet, dass das Gewichtsverhältnis des Übergangsmetalls des Metallocens zu dem Element der Gruppe IVB des katalytischen Feststoffs 0,05 bis 10 beträgt.
  21. Verfahren gemäß einem der Ansprüche 1 bis 20, dadurch gekennzeichnet, dass das neutrale Metallocen oder das Ionisierungsmittel auf einem mineralischen Träger abgeschieden ist.
  22. Verfahren gemäß einem der Ansprüche 1 bis 21, dadurch gekennzeichnet, dass der katalytische Feststoff mit einem mineralischen Träger gemischt wird, wobei das neutrale Metallocen anschließend zu diesem Gemisch hinzugefügt wird.
  23. Verfahren gemäß Anspruch 21 oder 22, dadurch gekennzeichnet, dass der mineralische Träger Siliciumdioxid, Aluminiumoxid, Magnesiumchlorid oder ein Gemisch von Siliciumdioxid und Magnesiumchlorid ist.
  24. Verfahren gemäß einem der Ansprüche 1 bis 23, dadurch gekennzeichnet, dass es auf die Herstellung von Homopolymeren des Ethylens oder des Propylens und von Copolymeren des Ethylens und/oder des Propylens angewandt wird.
EP98124378A 1992-12-17 1993-12-08 Verfahren zur (Co)Polymerisation von Olefinen Expired - Lifetime EP0908468B1 (de)

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EP93203437A EP0602716B1 (de) 1992-12-17 1993-12-08 Katalysatorsystem, Verfahren zur dessen Herstellung und seine Verwendung in der Olefinpolymerisation

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BR9305093A (pt) 1994-07-05
EP0602716A1 (de) 1994-06-22
DE69333535D1 (de) 2004-07-01
RU2145612C1 (ru) 2000-02-20
ES2217490T3 (es) 2004-11-01
TW332821B (en) 1998-06-01
CA2111369A1 (fr) 1994-06-18
JPH0710917A (ja) 1995-01-13
US5496782A (en) 1996-03-05
JP3466681B2 (ja) 2003-11-17
KR940014452A (ko) 1994-07-18
KR100291249B1 (ko) 2001-10-24
DE69327303D1 (de) 2000-01-20
US5719235A (en) 1998-02-17
DE69333535T2 (de) 2004-12-02
EP0602716B1 (de) 1999-12-15
ES2142330T3 (es) 2000-04-16
PT908468E (pt) 2004-08-31
PT602716E (pt) 2000-06-30
ATE187744T1 (de) 2000-01-15
EP0908468A3 (de) 2000-05-17
EP0908468A2 (de) 1999-04-14
DE69327303T2 (de) 2000-07-20
BE1006438A3 (fr) 1994-08-30
ATE267844T1 (de) 2004-06-15

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